Azodyestuffs insoluble in water and process of making same



Patented May 19, 1931 PATENT, OFFICE .LnoronnLAsKA, RUDoLF-nEYHnR, AND ARTHUR zrrsciinraor orFnNBAoH oN-rmn MAIN, GERELCANY, ASSIGNURS 'iQ ANILINE-VJGRKS, I1\TC., OF NEW YORK,

N. Y., A CORPORATION or DELAWARE AzoDYnsrUFFsINsoLUBLn In WATER AND PROCESS or MAninG SAME M No Drawing. Application filedollecember 11 1928, Serial No. 325,384, and in Germany December 12, 1927.

Our'present inventionrelatesto new azo dyestuffs insoluble in water, more particularly it relates to new azodyestuffs of the following general formula:

Hal X Y X NH:

X CH3 wherein one X represents halogen and the other Xs stand for hydrogen. 7

These new products are orange to claret red dyestuffs which surpass as to their fast- ,ness especially to light the corresponding dyestuffs containing only one halogen atomv in the 4 or 5 position in relation to the methox y group.

These combinations are of particular value for producing prints accordingto the well known rapide fast printing process i. e. the printing with a mixture of a nitro-saminealkali-salt and an arylide of the 2rhydroxy- 3-naphthoic acid, since they are fast to steaming even without any addition of chromate. They may also be employed as pigment dyestuffs and they may be produced on the fiber. Some of dyeings thus produced are distinguished by a remarkable fastness to the action ofcaustic soda solution.

paste.

ary manner show clear yellowish red shades.

In order to further illustrate our invention the following examples are given, the

parts being by weight and all temperatures I in centigrade degrees, but it may be understood that our invention is not limited to the particular productsor reacting condi- "j tions mentioned therein. I I

Ewample 1 19.2 parts of 4.6-di chloro-2-anisidine are diazotized in the customary manner and this diazo solution is combined with a solution of 29.1 parts of 2-hydroxy-3-naphthoyl-ttoluidine in a caustic soda solution containing Turkey red oil and an amount of sodium mineral acid. The dyestufl' precipitated is filtered off and well washed. It corresponds to the formula: 1

In order to prepare a lake therefromcit is advantageously applied in the form of a The lakes prepared in the customof a good fastness.

Example 2 Well boiled and dried cotton yarn is impregnated with a solution containing '9 grs.

acetate sufiicient for b1nd1ng the excess of p of 2-hydroXy-3-11aphthoyl-2-amino-1 ethylbenzene, 14 cc. of a caustic'soda solution of 35 B. and 8 cc. of Turkey red oil. per liter.

The yarn thus treated is well wrung outand the dyestuff is developed on the fiber with a diazo solution corresponding to 3.8grs. of 4.6- dichloro-2 anisidine per liter and nearly neu- B roducin the d estult on the fiber according to the rapide last printing process prlntlngs are obtained which show the same shade and are fast to steaming.

Example 3 A printing color is prepared in the usual manner from the following ingredients:

18 parts of 2 hydroxy-3-naphthoyl-1- amino-naphthalene 60 parts of Turkey red oil 20 parts of caustic soda solution of 37 B.

38 parts of an aqueous paste ot the nitrosamine potassium salt (prepared from 4.5-. dichloro-Q-anisidine for instance according to U. S. application Serial No. 240,632, filed December 16, 1927) containii'ig 32.1% of the corresponding amine and 14.44% of caustic potash,

36 l-parts of water 7 500 parts of neutral starch tragacanth thickening.

The goods are printed with this printing paste, steamed in the Mather-Flatt at 100 for about 3 minutes. After having passed a bath containing 30 cc'. of acetic acid of 6 B. and 50 grs. of Glaubers salt per liter and warmed to 80, they'are rinsed, soaped and dried.

In this manner clear claret red printings of a good fastness are obtained. The dyestufl thus produced on the fiber corresponds to the formula:

OCH;

Even when the dyestuff is accompanied in printing by other colors, which want a longer steaming for fixation, it can be printed without the shade being injured.

By producing the dyestuft on cotton yarn according to the ice-color method dyeings of the same shade are obtained having a very good fastness to kier boiling.

When using instead of the salt of nit-rosamine of 4.5-dichloro-2-anisidine the potassium salt of the nit-rosamine of 4-chloro-5- bromo-Q-anisidine and carrying out the process in the same manner as described above also a claret printing of a good fastness is obtained.

Our process may be carried out in the same way when starting from other arylides or 2- hydr0Xy-3naphthoic acid. For instance the diazocompound of 4.6-dichloro-2-ani'sidine yields when combined with the Q-hydroxy- 8-naphthoyl compound of V Aniline, bright orange red shades.

Q-toluidin'e, clear orange red shades.

Q-anisidine, orange red shades.

l-chloroanilin'e, yellowish red shades.

5-chloro-2-anisidine, yellowish red shades.

The diazocompound of 4:.5-dichloro-2-anisidine yields when combined with the Q-hydroXy-3-naphthoyl compound of 2-phenetidine, full bluish red shades.

a-phenetidine, wine red shades.

Q-anisidine, claret red shades.

l-chloro-Q-anisidine, wine red shades.

5-chloro-2-anisidine, bluish garnet shades. 5-chloro2-toluidine, wine red shades.

Amino-hydroquinone-dimethylether, wine red shades.

We wish it to be understood that in the following claims the term combining the components comprises everywhere combining in substance or on a substrate particularly on the fiber, for instance according to the icecolor method or to one of the usual printing processes.

WVe claim: I

1. As new compounds the azodyestufis of the probable formula Hal X ary1-HNOO wherein one X means halogen and the other 'X s mean hydrogen, which compounds are the probable formula:

1,806,915 i q I 3 2. Materials dyed or printed with the new which dyestuff is when dry a claret red powazodyestufis of claim 1 said dyestufls being der insoluble in water, yielding on reducproduced on these materials. tion 1-amino-2-hydroXy-3'-naphthoic acid (1-,

3. As new compounds the azodyestufls of naphthalide and 4L.5-dichloro-2-anisidine.

5 the probable formula: I r 8. Materials dyed or printed with the new Hal azodyestuff of claim 7 said dyestuif being i 1 I produced on these materials. Hal N: H a In testimony whereof, we aflix our signatures. 10 0H: LEOPOLD LASKA.

HO 7 RUDOLF REYI-IER.

ARTHUR ZITSCI-IER.

aryl-HN-O which compounds are when dry orange to claret red powders, insoluble in water, yielding on reduction an 1-amino-2-hydroXy-3- naphthoic acid arylide and a 4.5-dihalogeno- Q-anisidine of the formula:

Hal

produced on these materials.

5. As new compounds the azodyestufl's of aryl-HN-O 40 which compounds are when dry orange to 195 claret red powders, insoluble in water, yielding on reduction an 1-amino-2-hydroxy-3- naphthoio acid arylide and 4.5-dichloro-2- anisidine of the formula:

45 p I I I OFQNH.

6. Materials dyed or printed with the new azodyestuifs of claim 5'said dyestuifsbeing produced on these materials.

7 As a new compound the dyestufl' of the 55 probable formula:

HN-O i I 

